Aqueous formulation of fungicide in concentrated suspension, production process for said formulation and uses thereof

Abstract

The present invention relates to an aqueous formulation of a dithiocarbamate fungicide as a suspension concentrate (SC), as well as a process for producing said formulation. The formulation is specially applied to biological targets present in crops such as rice, bananas, potatoes, citrus fruits, beans, apples, corn, roses, soy, tomatoes, wheat and grapes. The formulation has the same or better physicochemical stability and efficacy compared to existing SC fungicide formulations, making it an alternative product for farmers. In this context, said formulation is free of a plurality of adjuvants, especially those defined as non-essential in the context of the present invention, and the adjuvants used are present in low concentrations. This formulation is also free of adjuvants that are toxic to biota, humans and the environment. The production process, in turn, is an additional differentiator in view of peculiarities such as the order in which the components are added, the nature of the steps, the order in which they are carried out, and the process variables involved.

Description

AQUEOUS FORMULATION OF FUNGICIDE IN CONCENTRATED SUSPENSION, PRODUCTION PROCESS OF SAID FORMULATION AND ITS USES

[0001] This invention patent application claims internal priority of process BR 10 2022 026950 5, filed on 12 / 29 / 2022, under Law No. 2 9,279, of May 14, 1996. FIELD OF APPLICATION

[0002] The present invention is contained in the field of application of agronomic engineering, agricultural engineering, organic chemistry, physical chemistry, chemical engineering, botany and biology.

[0003] More specifically, the present invention relates to an aqueous fungicide formulation in concentrated suspension comprising a dithiocarbamate active ingredient, the production process of said formulation and its agronomic uses. DESCRIPTION OF THE STATE OF THE TECHNIQUE

[0004] When it comes to agronomic formulations based on concentrated suspensions (SC), that is, containing active ingredients in high concentrations, one of the biggest challenges is the low physical-chemical stability, the reduced solubility of pesticides, such as dithiocarbamate fungicides, and sedimentation that leads to phase separation. In this context, there are aqueous formulations and oil dispersions (OD). In the latter, dithiocarbamates such as mancozeb are insoluble, which requires effort in the correct selection and quantity of adjuvants capable of providing the desired physical-chemical stability and, consequently, achieving high agronomic performance. This is because the added components are crucial to providing a stable composition, which would not be possible with the simple addition of the dithiocarbamate itself to the oil. On the other hand, aqueous concentrated suspensions are more viable compared to OD ones because dithiocarbamates have some solubility in this case, although reduced.

[0005] Clearly, concentrated OD and aqueous suspensions were developed for specific applications; that is, they were not developed to outperform one another. In fact, there are cases in which an aqueous suspension is more recommended than an OD suspension, and vice versa. In this sense, the present invention focuses strictly on solving prior art problems related to aqueous concentrated suspensions, the challenges of which will be described in more detail below.

[0006] Although dithiocarbamates, especially mancozeb, have low water solubility compared to predominantly hydrophobic solutions, this property is still insufficient for the formulation to achieve any agronomic performance. Therefore, even aqueous formulations face challenges related to physical-chemical stability, phase separation, and hydrolytic degradation. These problems are inherent to the intra- and intermolecular properties of mancozeb, which, as a compound based on zinc and manganese metals complexed with organic molecules based on a dithiocarbamate, constitutes a strongly ionic chemical species. More specifically, the ionic strength in this case hinders the breakdown of electrostatic interactions, which would favor easier dispersion of the compound. Consequently, this fungicide has low water solubility, despite being an ionic compound.This molecular property also explains the insolubility of mancozeb in oil, that is, it is a hydrophilic (ionic) compound that, as those skilled in the art know, is not soluble in hydrophobic solutions that constitute OD fungicide formulations.

[0007] That said, the main challenges related to Aqueous fungicide formulations in concentrated suspensions. In this context, the agricultural fungicide inputs market is directing efforts toward the continued development of liquid mancozeb in concentrated suspensions, reflecting the plurality of patent and scientific prior art on this topic. When the focus is on resolving physical-chemical stability issues, which is one of the properties that directly impact application results, aqueous fungicide formulations in concentrated suspensions are developed through the selection of appropriate adjuvants and their respective concentrations. In this context, there is a multitude of choices for dispersants, thickeners, surfactants, preservatives, humectants, etc., and therefore, each formulation is generally unique.

[0008] In the prior art closest to the present invention, prior art describes formulations presenting problems such as the use of components that promote dithiocarbamate agglomeration, especially mancozeb, and heavy aromatic adjuvants derived from petroleum, which are harmful to the environment and significantly toxic to professionals handling the product in the field, as well as to producers. Furthermore, SC aqueous fungicide formulations often contain a variety of secondary components that do not affect the efficacy of the active ingredient; that is, they are used as preservatives and related substances. Although they may indirectly contribute to the final properties of the formulation, some components may be unnecessary, such as pH regulators and toxic solvents. Specifically, in the case of preservatives, these do not contribute to efficacy and can impair the biological action of the active ingredient.Ideally, it is desirable to have the smallest amount (or absence) of adjuvants in agrochemical formulations while maintaining efficiency of use, especially when components are harmful to the environment. Toxic to humans and living beings are included. Therefore, simple formulations free of toxic components are a common goal in the fungicide market, with increasing efforts being made to develop efficient, low-toxic, simple, and environmentally sound formulations.

[0009] Still regarding prior art issues, especially regarding documents describing aqueous formulations of mancozeb as the sole active ingredient and in the form of a concentrated suspension, it is common to find teachings on the use of xanthan gum as a thickener. The use of this adjuvant promotes high viscosity in formulations (an inherent property of this polysaccharide) and, therefore, hinders processing of the product during its manufacture and use due to its high flow resistance. Xanthan gum is a polysaccharide based on D-glucose units in the main chain, said main chain being anchored by trisaccharide-based side chains, and said trisaccharide consisting of two mannose units separated by a glucuronic acid unit.The side chain of this gum provides the aforementioned high viscosity due to intermolecular steric effects, reducing movement between the polysaccharide polymer chains. Similarly, steric effects extend to the formulation's dispersant polymers, hindering their fluidity and, therefore, reducing the dispersion-enhancing effect of fungicidal particles—mancozeb particles, for example. To solve this problem, highly concentrated dispersants are commonly used to improve fluidity. Because of this property, in addition to requiring a high amount of the adjuvant, the polysaccharide also limits the use of more than one type of dispersant, which would be desirable from the standpoint of cooperative dispersant effects due to the presence of more than one. a dispersant polymer.

[0010] When it comes to production processes for aqueous fungicide suspension concentrate formulations, these often involve few steps involving the mixing of components simultaneously. This negatively impacts the properties of the final formulation, as there is no effective control over homogeneity in these cases, which directly affects the achievement of a finely divided dithiocarbamate dispersion and, consequently, application efficacy. Although the number of steps is reduced for most prior art processes, mancozeb fungicide formulations require greater process robustness to obtain a homogeneous fluid comprising finely divided material. Furthermore, existing production processes lack ongoing quality control monitoring, increasing the likelihood of obtaining non-standardized formulations and presenting the aforementioned technical deficiencies.For a better understanding of the problems of the state of the art mentioned herein, the prior art closest to the present invention will be described below, which reveal technologies presenting the problem discussed herein.

[0011] Document CN111972409 describes an aqueous formulation of mancozeb in concentrated suspension, and a process for producing said formulation. Among the preferred embodiments closest to the present invention is a formulation comprising siloxane, concentrated mancozeb, dispersant based on a high molecular weight surfactant, sodium lignosulfonate, propylene glycol and citric acid. The technology disclosed in this document is provided with two types of dispersants that, when added together, total a high concentration in the formulation (at least 10% by mass). Although there are two dispersants, they are present in high concentrations. quantity, highlighting the problem related to the high amount of adjuvants used to obtain formulations that achieve the target physicochemical properties. More specifically, there is the problem of toxicity inherent to adjuvants; that is, the greater the amount, the greater the toxicity of the formulation as a whole. For comparison purposes, the toxicological effects of the active ingredient itself should be disregarded, since in the field of the present invention, mancozeb in prior art formulations presents similar and high concentration ranges, as they fall within the context of concentrated suspension formulations. More specifically, the toxicological contribution of this dithiocarbamate in the formulations known herein and in that of the present invention is the same.Therefore, the technical problem with formulations such as those described in CN111972409 also resides in the high concentration of adjuvants in the formulation as a whole, which requires efforts to reduce them and, simultaneously, maintain the final physical-chemical properties, whether they are equal to or better than what already exists.

[0012] Still regarding document CN111972409, this reveals the SC formulation comprising adjuvants that do not contribute to agronomic performance, being included only to maintain its desired properties. These include the antifreeze component (preferably propylene glycol) and pH regulator (citric acid and related compounds). Furthermore, propylene glycol is found in high quantities in all formulations described as preferred, at 12% by mass.

[0013] Document CN115067327 discloses a fungicide composition for slow release of mancozeb, said composition comprising the following components in percentage by mass: technical mancozeb 20-30%; slow release agent 5-8%; dispersant 5-8%; suspending agent 1-2%; antifoaming agent 0.5%-1%; preservative 0.1-0.3%; antifreeze 1-5%; and deionized water making up 100%. In a first aspect, the composition described in this prior art comprises dispensable adjuvants, that is, they are included only to maintain the final properties of the formulation, not contributing directly to its application effectiveness, said dispensable adjuvants being the antifreeze propylene glycol (2% in a preferred composition and closest to the present invention) and preservative carbazone (0.2% in a preferred composition and closest to the present invention). In a second aspect, said formulation comprises a dispersant which, in a preferred embodiment and closest to the present invention, is a polyoxypropylene / polyoxyethylene copolymer and in high concentration.In this context, in addition to this adjuvant being present in a considerable quantity, which significantly contributes to the toxicity of the formulation as a whole, it is the only dispersant present in the product. Thirdly, the composition described in this document comprises a mancozeb release agent. In this context, the technology described in CN115067327 focuses on solving the problem of the lack of control over mancozeb absorption; that is, it has a different direction than the present invention. The composition production process, in turn, comprises few steps involving the mixing of almost all components simultaneously, and these steps are not monitored from a quality control perspective.

[0014] Document IN-234049 discloses an aqueous formulation of mancozeb in concentrated suspension comprising xanthan gum as a thickener, sodium metabisulfite and hexamethylene tetramine (HMT) preservatives, dispersants such as naphthalene sulfonic acid condensate with formaldehyde and sodium lignosulfonate, ethylene glycol antifreeze and mineral oil. Although it uses two dispersant components in small quantities, namely the aforementioned naphthalene-based components and lignosulfonate, these components, when used simultaneously in the same formulation, promote poor physical and chemical stability, as taught in US4804399. Furthermore, components based on naphthalene derivatives are significantly toxic to humans, biota, and the environment. Additionally, the mentioned formulation contains xanthan gum, which, as mentioned, reduces the fluidity of the dispersant agents, affecting their dispersion properties. Still regarding the use of this gum, document US4804399 also discloses that the use of polysaccharide gums in concentrated aqueous suspensions favors the formation of viscous sediments, posing an additional problem with regard to the physical and chemical stability of the composition.Finally, the concentration of xanthan gum in the IN-234049 formulation, predominantly in the embodiment examples, is significantly low, which reduces the final viscosity. Low-viscosity formulations, when applied, have the disadvantage of reduced exposure time of the active ingredient to the biological target due to a higher likelihood of leaching. Finally, IN-234049 also describes a formulation production process involving few steps in which the components are mixed in a single step and lacks effective quality control to obtain standardized products.

[0015] Thus, the prior art would clearly benefit from an aqueous fungicide formulation in concentrated suspension comprising few adjuvants, said adjuvants in low concentration, free of non-essential components such as preservatives, antifreeze and related agents, and free of xanthan gum, said formulation being stable from a physicochemical point of view and efficient in application. Furthermore, the prior art also would have the benefits of a formulation free of components that are toxic to humans, the environment, and living beings, such as those derived from petroleum (heavy aromatic solvents, naphthalene, paraffin, hydrocarbons in general, etc.). In this sense, the present invention provides an alternative formulation, comprising results equal to or better than those already existing, with the technical difference mentioned above and, also, as a low-cost option.

[0016] Furthermore, an additional benefit of the present invention is a process for producing the aqueous formulation of fungicide in concentrated suspension, said process benefiting the state of the art by including a plurality of steps and quality control essential for obtaining a stable, efficient and standardized formulation. BRIEF DESCRIPTION OF THE INVENTION

[0017] In a first aspect, the present invention relates to an aqueous fungicide formulation in concentrated suspension, said formulation comprising the following components, in mass percentage (% m / m): (a) 30 to 50% of a dithiocarbamate fungicide; (b) 0.1 to 3% of a first dispersant, said first dispersant being an aliphatic ethoxylated alcohol of formula (I) Ri-O-(CH2CH2O) n -H (I), where Ri is a linear or branched C8-C25 alkyl chain and "n" ranges from 1 to 10; (c) 0.1 to 3% of a second dispersant, said second dispersant being a block copolymer of polyethylene glycol and polypropylene glycol of formula (II) H-[OCH2CH2]x[OCH(CH3)CH2]y[OCH2CH2]x-OH (II), where "x" varies from 80 to 135 and "y" varies from 30 to 70; (d) 0.1 to 2% of a thickener, said thickener being a cellulose derivative; (e) 0.1 to 3% of an antifoam; and (f) 50 to 65% water, said formulation being free of any of the following components: (A) polysaccharide gum; (B) naphthalene derivatives; (C) pH regulators; (E) antifreeze; (F) hydrocarbons derived from petroleum; (G) lignosulfonate salts; and (H) formaldehyde.

[0018] In a second aspect, the present invention relates to a process for producing the aqueous fungicide formulation in aqueous suspension as described herein, said process comprising the following steps: (a) in a formulating tank, add water and start stirring using a mixer; (b) add the aliphatic ethoxylated alcohol of formula (I) to the water and continue stirring; obtaining a first mixture; (c) add the polyethylene glycol and propylene glycol block copolymer of formula (II) to the first mixture and continue stirring; obtaining a second mixture; (d) add the antifoaming agent to the second mixture and keep stirring; obtaining a third mixture; (e) add the dithiocarbamate to the third mixture, said addition being carried out between 30 and 120 minutes, preferably 60 minutes, and keep stirring after the time of addition of said dithiocarbamate; obtaining a fourth mixture; (f) grinding the fourth mixture for 60 to 180 minutes, preferably 90 minutes, said grinding being carried out at temperatures between 20 and 30 °C, preferably 25 °C, and said grinding being carried out at a rotation frequency between 20 and 80 Hz, preferably between 30 and 70 Hz, more preferably between 40 and 60 Hz; obtaining a ground mixture comprising dithiocarbamate microparticles; (g) carrying out a preliminary quality control of the ground mixture, said quality control comprising a particle size analysis (dgs) and a 325 mesh test for dithiocarbamate microparticles; (h) decision on repeating step (f) or proceeding with step (i), said decision being based on the following conditions: if the particle size (dgs) is outside the range between 2 and 7 microns, repeat step (f); if the particle size (dgs) is between 2 and 7 microns and the 325 mesh test shows zero or negligible retention of said microparticles, proceed with step (i); (i) add the cellulose derivative and the preservative to the mixture approved in step (h), and start stirring; obtaining the aqueous fungicide formulation in concentrated suspension; and (j) carrying out a general quality control comprising the measurement of physicochemical parameters selected from the group comprising color, pH, density, foam, viscosity, particle size, 325 mesh test, 200 mesh test, suspensibility, mancozeb content and stability at 54°C, said parameters comprising the specifications described in table 2, said specifications defining the quality conditions under which the formulation obtained will present the desired physical-chemical properties for effective agronomic performance.

[0019] In a third aspect, the present invention relates to the use of the aqueous fungicide formulation in aqueous suspension for application to biological targets present in crops selected from the group comprising rice, banana, potato, citrus, beans, apple, corn, rose, soybean, tomato, wheat, grape, sugar cane or cotton. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] The subject matter of this Invention will become completely clear in its technical aspects from the detailed description that will be made based on the figures listed below, in which:

[0021] Figure 1: Flowchart of the production process of the aqueous fungicide formulation in concentrated suspension. DETAILED DESCRIPTION OF THE INVENTION

[0022] In accordance with the objectives presented in the brief description, in a first aspect the present invention relates to an AQUEOUS FORMULATION OF CONCENTRATED SUSPENSION FUNGICIDE, said formulation comprising the following components, in mass percentage (% m / m): (a) 30 to 50% of a dithiocarbamate fungicide; (b) 0.1 to 3% of a first dispersant, said first dispersant being an aliphatic ethoxylated alcohol of formula (I) Ri-O-(CH2CH2O) n -H (I), where Ri is a linear or branched Cs-C25 alkyl chain and "n" ranges from 1 to 10; (c) 0.1 to 3% of a second dispersant, said second dispersant being a block copolymer of polyethylene glycol and polypropylene glycol of formula (ID H-[OCH2CH2]x[OCH(CH3)CH2]y[OCH2CH2]x-OH (II), where "x" varies from 80 to 135 and "y" varies from 30 to 70; (d) 0.1 to 2% of a thickener, said thickener being a cellulose derivative; (e) 0.1 to 3% of an antifoam; and (f) 50 to 65% water, said formulation being free of any of the following components: (A) polysaccharide gum; (B) naphthalene derivatives; (C) pH regulators; (E) antifreeze; (F) hydrocarbons derived from petroleum; (G) lignosulfonate salts; and (H) formaldehyde.

[0023] For a better understanding of the present invention, it should be understood that the fungicide dithiocarbamate is an active ingredient in the aqueous fungicide suspension concentrate formulation, and that the other components are referred to as adjuvants. In this sense, the active ingredient and adjuvant are each referred to as components of said formulation. Also for a better and more accurate understanding of what is described in this report, adjuvants are components that are mixed with the active ingredient to improve its agronomic efficacy.

[0024] For the purpose of better understanding the present invention, the present described as "aqueous fungicide formulation in concentrated suspension" will alternatively be described simply as "formulation". Therefore, whenever "formulation" is mentioned, it should be understood that it refers to the "aqueous fungicide formulation in concentrated suspension".

[0025] In a non-restrictive embodiment of the present invention, the formulation comprises the following components, in mass percentage (% w / w): (a) 35 to 45% of the dithiocarbamate fungicide, preferably 38.2%; (b) 0.8 to 1.5% of the aliphatic ethoxylated alcohol of formula (I), preferably 1.3%, (c) 0.8 to 1.5% of the block copolymer of polyethylene glycol and polypropylene glycol of formula (II), preferably 1.4%; (d) 0.1 to 1% of the cellulose derivative, preferably 0.2%; (d) 0.1 to 1% of the antifoam, preferably 0.9%; and (e) 55 to 60% water, preferably 58%.

[0026] In a non-restrictive embodiment of the present invention, Ri is a linear C10-C20 alkyl chain, preferably a linear C12-C16 alkyl chain, "n" ranges from 1 to 6, preferably from 1 to 3, "x" ranges from 90 to 110, preferably from 95 to 100, and "y" ranges from 55 to 70, preferably from 62 to 67.

[0027] In a non-restrictive embodiment of the present invention, the formulation additionally comprises a preservative in low concentration, said preservative being present in the formulation in amounts between 0.001 and 0.01% by mass (% m / m), preferably 0.005% (m / m).

[0028] In a non-restrictive embodiment of the present invention, the dithiocarbamate is selected from the group comprising mancozeb, maneb, metiram, propineb, zineb, amobam, ferbam, thiram or ziram, preferably mancozeb.

[0029] In a non-restrictive embodiment of the present invention the cellulose derivative is selected from the group comprising methyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, hydroxyethyl carboxymethyl cellulose, carboxymethyl cellulose or carboxymethyl hydroxyethyl cellulose, preferably hydroxyethyl cellulose.

[0030] In a non-restrictive embodiment of the present invention, the defoamer is a silicone emulsion.

[0031] In a non-restrictive embodiment of the present invention, the preservative is selected from the group comprising 2-methyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one or n-octyl-isothiazolin-3-one, preferably 1,2-benzisothiazolin-3-one.

[0032] In a non-restrictive embodiment of the present invention, the polysaccharide gum is selected from the group comprising xanthan gum, guar gum, locust bean gum, tragacanth gum, gum arabic, gellan gum, carrageenan gum, ghatti gum or karaya gum, preferably xanthan gum.

[0033] In a non-restrictive embodiment of the present invention, the naphthalene derivatives are selected from the group comprising naphthalene, condensate of naphthalene sulfonic acid with formaldehyde, condensate of diisopropyl naphthalene sulfonic acid with formaldehyde, condensate of alkyl naphthalene sulfonic acid with formaldehyde, naphthalene sulfonic acid, sodium naphthalene sulfonate, diisopropyl naphthalene sulfonic acid, diisopropyl naphthalene sulfonate sodium, alkyl naphthalene sulfonic acid or sodium alkyl naphthalene sulfonate, preferably condensate of naphthalene sulfonic acid with formaldehyde, naphthalene sulfonic acid or sodium naphthalene sulfonate.

[0034] In a non-restrictive embodiment of the present invention, the pH regulators are selected from the group comprising propionic acid, sorbic acid, benzoic acid, citric acid, lactic acid or acetic acid, preferably citric acid.

[0035] In a non-restrictive embodiment of the present invention, the antifreezes are preferably antifreeze glycols, said antifreeze glycols being selected from the group comprising propylene glycol, ethylene glycol, polyethylene glycol or glycerol, preferably propylene glycol or ethylene glycol.

[0036] In a non-restrictive embodiment of the present invention, the petroleum-derived hydrocarbons are selected from the group comprising aromatic solvents, naphthalenic solvents, naphthalenic oils or paraffinic oils.

[0037] In a non-restrictive embodiment of the present invention, the lignosulfonate salts are selected from the group comprising sodium, calcium or ammonium lignosulfonate, preferably sodium lignosulfonate.

[0038] Among the components cited as absent in the aqueous suspension fungicide concentrate formulation, formaldehyde is the only one specifically described, i.e., not belonging to a group of related components such as those in items (A)-(G). This is because formaldehyde is a significantly toxic compound, recognized as carcinogenic, mutagenic, and harmful to the skin. Therefore, this component is strictly controlled by numerous regulatory agencies worldwide, such as in Brazil. Thus, unlike numerous SC aqueous dithiocarbamate formulations known in the art, the formulation of the present invention does not contain formaldehyde.

[0039] Considering the complete description of the formulation, whether from the point from the point of view of the components themselves and their respective quantities, their difference in relation to the state of the art is crystal clear, for the reasons that will be described below.

[0040] Initially, the formulation lacks non-essential adjuvants, such as pH regulators, antifreeze, buffers, preservatives, and related substances. This is because these components are not included to improve agronomic performance; that is, they do not alter the active ingredient's biological mechanisms of action in the target organism. In this context, these components are included in prior art formulations solely to maintain their physicochemical and agronomic properties, properties provided by the essential adjuvants referred to herein, namely dispersants, antifoams, surfactants, humectants, and thickeners.These essential adjuvants improve stability, biological availability, exposure time of the active ingredient to the target organism and leaf surface, and resistance to decomposition during the residence time after application. These properties are often maintained and controlled by non-essential adjuvants, which, in the aqueous suspension concentrate fungicide formulation, are dispensable, so their absence does not reduce effectiveness. In fact, the inventors of the present invention surprisingly designed the formulation to be free of these non-essential adjuvants due to the nature of the components chosen and their respective quantities. Although the absence of the preservative in the formulation was mentioned when it is in fact present, its concentration is irrelevant because it is present in amounts between 0.001 and 0.01% by weight (% w / w), preferably 0.005%.Compared to prior art formulations, preservatives are 100 times more concentrated compared to the present invention and the amount of. The preservative content of the formulation is negligible, having no effect on its ability to preserve and maintain the properties of said formulation over time. Therefore, the minimal inclusion of the preservative in no way contributes to the preservative effect that is necessary for prior art formulations and dispensable in the present invention. The preservative was included in this insignificant concentration because it is contained in the cellulose derivative (preferably hydroxyethyl cellulose). More specifically, the cellulose derivative is a preformulation of cellulose derivative + preservative, with said preservative being essential only for the cellulose derivative prior to its addition to the formulation.

[0041] Secondly, the aqueous suspension fungicide formulation is free of polysaccharide gum, especially xanthan gum. This is because this component, often used as a thickener, reduces the fluidity of dispersants and, consequently, reduces their physicochemical stability. Furthermore, polysaccharide gums in general, such as those mentioned above, preferably xanthan gum, are known to promote sedimentation in superconcentrated fungicide formulations, especially aqueous ones containing dithiocarbamates such as mancozeb.

[0042] Considering the above, the aqueous fungicide suspension concentrate formulation contains only a few essential adjuvants, said to be adjuvants in small quantities, with low intrinsic toxicity and environmental friendliness. Despite these characteristics, the formulation surprisingly demonstrated physical and chemical stability and agronomic performance equal to or better than prior art formulations. Consequently, in addition to solving the technical problems described, this formulation also offers consumers an alternative from a safety perspective. economical, since only 4% (w / w) of the formulation constitutes the aforementioned adjuvants. In this context, although the demand for mancozeb is similar to that of existing SC formulations, the need for adjuvants is significantly reduced, reducing consumption. The amount of adjuvants that was eliminated in the present invention is replaced by water.

[0043] In a second aspect, the present invention relates to a PROCESS FOR PRODUCTION of the aqueous fungicide formulation in aqueous suspension as described herein, said process comprising the following steps: (a) in a formulating tank, add water and start stirring using a mixer; (b) add the aliphatic ethoxylated alcohol of formula (I) to the water and continue stirring; obtaining a first mixture; (c) add the polyethylene glycol and propylene glycol block copolymer of formula (II) to the first mixture and continue stirring; obtaining a second mixture; (d) add the antifoaming agent to the second mixture and keep stirring; obtaining a third mixture; (e) add the dithiocarbamate to the third mixture, said addition being carried out between 30 and 120 minutes, preferably 60 minutes, and maintain stirring after the time of addition of said dithiocarbamate; obtaining a fourth mixture; (f) grinding the fourth mixture for 60 to 180 minutes, preferably 90 minutes, said grinding being carried out at temperatures between 20 and 30 °C, preferably 25 °C, and said grinding being carried out at a rotation frequency between 20 and 80 Hz, preferably between 30 and 70 Hz, more preferably between 40 and 60 Hz; obtaining a ground mixture comprising dithiocarbamate microparticles; (g) carrying out a preliminary quality control of the ground mixture, said quality control comprising a particle size analysis (dgs) and a 325 mesh test for dithiocarbamate microparticles; (h) decision on repeating step (f) or proceeding with step (i), said decision being based on the following conditions: if the particle size (dgs) is outside the range between 2 and 7 microns, repeat step (f); if the particle size (dgs) is between 2 and 7 microns and the 325 mesh test shows zero or negligible retention of said microparticles, proceed with step (i); (i) add the cellulose derivative and the preservative to the mixture approved in step (h), and start stirring; obtaining the aqueous fungicide formulation in concentrated suspension; and (j) carrying out a general quality control comprising the measurement of physicochemical parameters selected from the group comprising color, pH, density, foam, viscosity, particle size, 325 mesh test, 200 mesh test, suspension level, mancozeb content and stability at 54°C, said parameters comprising the specifications described in table 2, said specifications defining the quality conditions by which the formulation obtained herein will present the desired physicochemical properties for effective agronomic performance.

[0044] It should be understood that the dithiocarbamate, the aliphatic ethoxylated alcohol of formula (I), the block copolymer of polyethylene glycol and propylene glycol of formula (II), the cellulose derivative, the antifoam and the preservative mentioned in the description of the production process of the aqueous formulation of fungicide in concentrated suspension are as described in this descriptive report, especially in the description of the formulation. Thus, the components mentioned in this embodiment of the invention must be interpreted based on what has already been described, and a replicated description below is unnecessary.

[0045] In the following description, one of the aspects that will be mentioned is the quantities added of the components during steps (a) to (j). In this sense, these quantities are those specified for the formulation itself. In other words, they refer to the quantities of the components in the final formulation, as described here and as shown in Table 1.

[0046] The agitation mentioned throughout steps (a) to (j) in any of the embodiments described herein is performed by a stainless steel mixer equipped with a disc-type (shear) agitation system. In this context, the agitation speed is controlled until a vortex forms, which is within the knowledge of a person skilled in the art. In a non-restrictive embodiment of the present invention, the agitation mentioned in any of the steps described herein is performed at speeds between 300 and 800 rpm, preferably between 300 and 600 rpm, more preferably between 300 and 400 rpm, said agitation being performed at a temperature of 13 to 37°C, preferably 25°C.

[0047] In a non-restrictive embodiment of the present invention, the agitation mentioned in steps (a), (b) and (c) is carried out for 1 to 40 minutes, preferably for 5 to 25 minutes, more preferably for 10 minutes.

[0048] In a non-restrictive embodiment of the present invention, the agitation mentioned in step (d) is carried out for 1 to 20 minutes, preferably for 1 to 10 minutes, more preferably for 5 minutes.

[0049] In a non-restrictive embodiment of the present invention, the stirring mentioned in step (e) is carried out for 3 to 120 minutes, preferably for 15 to 60 minutes, more preferably for 30 minutes.

[0050] In a non-restrictive embodiment of the present invention, the agitation mentioned in step (i) is carried out for 1 to 60 minutes, preferably for 8 to 30 minutes, more preferably for 15 minutes.

[0051] In step (a) water is added in quantities between 55 and 60% (m / m), preferably 58% (m / m).

[0052] In step (b) the aliphatic ethoxylated alcohol of formula (I) is added in quantities between 0.8 and 1.5% (m / m), preferably 1.3% (m / m). The first mixture now formed in this step comprises water and said aliphatic ethoxylated alcohol of formula (I).

[0053] In step (c) the block copolymer of polyethylene glycol and propylene glycol of formula (II) is added in quantities between 0.8 and 1.5% (w / w), preferably 1.4% (w / w). The second mixture formed in this step comprises water, aliphatic ethoxylated alcohol of formula (I) and said block copolymer of polyethylene glycol and propylene glycol of formula (II).

[0054] In step (d) the defoamer is added in quantities between 0.1 and 1% (w / w), preferably 0.9% (w / w). The third mixture formed in this step comprises water, aliphatic ethoxylated alcohol of formula (I), polyethylene glycol and propylene glycol block copolymer of formula (II), and said defoamer.

[0055] In step (e) the dithiocarbamate is added in quantities between 35 and 45% (w / w), preferably 38.2% (w / w). The fourth mixture formed in this step comprises water, aliphatic ethoxylated alcohol of formula (I), block copolymer of polyethylene glycol and propylene glycol of formula (II), antifoaming agent and said dithiocarbamate.

[0056] Step (f) is optionally performed using alternative state-of-the-art methods, provided that the dithiocarbamate has a particle size (dgs) between 2 and 7 microns, and is not retained in a 325 mesh.

[0057] Still in relation to step (f), grinding can be carried out in three types of mill, namely: vertical immersion mill (laboratory scale); horizontal pearl mill (production); or vertical immersion mill (production).

[0058] In step (i) the cellulose derivative is added in quantities between 0.1 and 1% (m / m), preferably 0.2% (m / m). The preservative, in turn, is added in quantities between 0.001 and 0.01% by mass (m / m), preferably 0.005% (m / m).

[0059] Step (j) is essential and one of the main differentiators of the production process of the formulation described herein, since it is directly correlated with the agronomic performance and standardization of the resulting product. More specifically, this step determines the specifications that the formulation must meet so that the surprising technical effect discovered by the inventors of the present invention can be achieved by a person skilled in the art, having access to the present description of the descriptive report.

[0060] As noted, the production process described herein comprises a plurality of steps, including the individual addition of each component, followed by stirring, and so on. Unlike the prior art, in which the processes involve the simultaneous addition of components in a respective step, in the present invention, such additions occur individually and successively, constituting a differential. Since mancozeb, the preferred dithiocarbamate of the present invention, has low solubility in water and is also prepared at high concentrations, the production process described provides individualized steps, favoring greater homogeneity and ease of dispersion. This characteristic is contributed by the order of addition for each of the components, which will be further described below.

[0061] The initial addition of the aliphatic ethoxylated alcohol of formula (I) to water and the polyethylene glycol and propylene glycol block copolymer of formula (II) is essential for a homogeneous premix. This is because the hydrophilic portion of these components comprises hydroxyl groups that interact strongly with water through hydrogen bonds, forming stable micelles. This is corroborated by the fact that each of these components is added individually; that is, the aliphatic ethoxylated alcohol of formula (I) is added first, followed by stirring. At this point, a homogeneous and stable mixture is obtained. Subsequently, this copolymer is added, followed by stirring. In this situation, the aforementioned hydrogen interactions occur, favoring the subsequent addition of the defoamer, which acts as a surfactant along with the two components mentioned above, as these three components each have a hydrophilic and a hydrophobic portion.

[0062] The dithiocarbamate is then added using a specific procedure. The addition is gradual and should be carried out within the time frame stated above, preferably according to the preferred process example described below. Gradual addition following the aforementioned addition time favors easy solubilization of the active ingredient as it is incorporated into the fluid. Therefore, the inventors of the present invention have discovered that the stirring time can be the one already stated in the process description or that in the preferred embodiment below. After this step, the dithiocarbamate is relatively stable from a physical standpoint. chemical. To further improve this property, a grinding step was necessary, provided the conditions described above were respected, preferably those in the embodiment examples below. Only at the end of the process is the thickener added, once the fluid is already homogeneous within what was surprisingly discovered by the inventors.

[0063] The resulting formulation must meet the specifications described in Table 2 to ensure the agronomic performance achieved. It is important to note that, in addition to the inherent characteristics of the production process described above, the formulation must include the components described herein, and also at the concentrations determined in the present invention. A person skilled in the art who replaces each of these components, removes, adds, and / or alters the concentration, will also need to develop a new production process. In other words, the nature of the aqueous suspension fungicide formulation and its production process are directly dependent, constituting a mutual advantage for obtaining an effective product. Thus, the technical difficulty of the present invention is clear regarding the design of a formulation with the aforementioned advantage and with performance equal to or better than the prior art.

[0064] In a third aspect, the present invention relates to the USE of the aqueous fungicide formulation in aqueous suspension for application to biological targets present in crops selected from the group comprising rice, banana, potato, citrus, beans, apple, corn, rose, soybean, tomato, wheat, grape, sugar cane or cotton.

[0065] For each of the crops mentioned above, the respective biological targets are as described in italics below: (a) rice: Pyricularia grisae, which causes rice blast disease; (b) banana: Mycosphaerella musicola, which causes Sigatoka disease; and Mycosphaerella fijiensis, which causes Black Sigatoka disease; (c) potato: Alternaria solanum, which causes early blight disease; and Phytophthora infestans, which causes late blight disease; (d) citrus: Phyllocoptruta oleivora causing the disease False Rust Mite; Diaporthe citri causing the disease Melanosis; and Elsinoe australis causing the disease Verrugosis; (e) beans: Colletotrichum lindemutianum, which causes Anthracnose disease; (f) apple: Venturia inaequalis for Scab disease; and Colletotrichum gloeosporioides for Bitter rot disease; (g) corn: Phaeosphaeria maydis for white spot disease; Puccinia polysora for corn rust disease; and Cercospora zeae maydis for Cercospora zeae disease. (h) pink: Diplocarpon rosae for Black spot disease; (i) soybean: Septaria glycines for Brown Spot disease; Corynespora cassiicola for Target Spot disease; Phakopsora pachyrhizi for Asian rust; and Colletotrichum truncatum for anthracnose disease; (j) tomato: Alternaria solan! for early blight disease; and Phytophthora infestans for late blight disease; (k) wheat: Bipolaris sorokiniana for Helminthosporiosis disease; and Pyricularia grisea for Blast disease; (l) grape: Plasmopora viticola for Downy Mildew disease; (m) sugarcane: Thielaviopsis paradoxus for pineapple rot disease; and Puccinia Kuehnii for orange rust disease; and (n) cotton: Corynespora cassiicola for target spot disease; and Ramularia areola for cotton ramularia disease.

[0066] Considering the above, the aqueous fungicide formulation in concentrated suspension is applied to selected biological targets from the group comprising Pyricularia grisae, Mycosphaerella musicola, Mycosphaerella fijiensis, Alternaria solani, Phytophthora infestans, Phyllocoptruta oleivora, Diaporthe citri, Elsinoe australis, Colletotrichum lindemutianum, Venturia inaequalis, Colletotrichum gloeosporioides, Phaeosphaeria maydis, Diplocarpon rosae, Septaria glycines, Corynespora cassiicola, Alternaria solani, Bipolaris sorokiniana, Plasmopora viticola, Greeneria uvicola, Phakopsora pachyrhizi, Colletotrichum truncatum, Thielaviopsis paradoxo, Puccinia Kuehnii, Puccinia polysora, Cercospora zeae maydis, Corynespora cassiicola or Ra mu la ria areola. As the description itself suggests, these biological targets are fungi present in these crops, these fungi causing, respectively, the aforementioned diseases. Examples

[0067] The following will describe preferred examples through which the present invention is conceived by those skilled in the art. However, such examples do not limit the scope of protection of the present invention and are disclosed here only for the purpose of better understanding it. Example 1

[0068] A preferred and non-restrictive example of the present invention is the aqueous fungicide formulation in concentrated suspension comprising the components and respective concentrations as described in Table 1.

[0069] Table 1: Aqueous fungicide formulation in concentrated suspension in a preferred example, said example showing the respective concentrations (C) of each of the components and their functions. (C) (C) (C) CAS Component Function (% m / V) (g / L) (% m / m) Water 7732-18-5 Solvent 67.35 673.5 57.925 Aquiloxypolyethyleneoxieta 68551-12-2 Dispersant 1 1.5 15 1.3 nol alcohol polyether Polyethylene copolymer- 9003-11-6 Dispersant 2 1.7 17 1.4 polypropylene glycol 159002-21-8 + Antifoaming silicone emulsion 1.0 10 0.86 25322-69-4 Mancozeb TC - Ingredient purity 94-75-7 44.5 445 38.3 greater than 85% active 2-hydroxyethyl ether 9004-62-0 Thickener 0.24 2.4 0.21 cellulose l,2-Benzisothiazolin-3- 2634-33-5 Preservative 0.006 0.06 0.005 one

[0070] The alkyloxypolyethyleneoxyethanol polyether alcohol is preferably of the brands Genapol LA 070 or Dehydol LT7.

[0071] The polyethylene-polypropylene glycol copolymer is preferably of the Genapol PF 40 or Pluronic PE 6400 brands.

[0072] The silicone emulsion is preferably from the brands SAG 1572, STRUKTOL SB 2071, AE SILAGRO 100 or TL-56N.

[0073] 2-hydroxyethyl cellulose ether is preferably NatrosolTM 250 brand.

[0074] 1,2-Benzisothiazolin-3-one is preferably from the brand Proxel GL 20; Acticide DB20; Nipacide BIT 20; IPEL BP 20. Example 2

[0075] For the purposes of better understanding this example, which refers to the description of the production process of the aqueous formulation of fungicide in aqueous suspension, the quantities of the components described herein are exactly those as described in table 1, and in any of the units of measurement specified herein (% m / m, % m / V or g / L).

[0076] In this preferred and non-restrictive example, the process of producing the aqueous fungicide formulation in concentrated suspension comprises the following steps: (1) add water to a mixer on the production line, said water being added in the amount specified in Table 1, and start stirring at a rate of 300 rpm at 25 °C; (2) add the alkyloxypolyethyleneoxyethanol polyether alcohol, and stir the mixture for 10 minutes while maintaining the stirring rate at 300 rpm at 25 °C - the amount of alkyloxypolyethyleneoxyethanol polyether alcohol is that as specified in Table 1; (3) add the polyethylene-polypropylene glycol copolymer, and stir the mixture for 10 minutes while maintaining the stirring rate at 300 rpm at 25 °C - the amount of polyethylene-polypropylene glycol copolymer is that specified in Table 1; (4) add the silicone emulsion, and stir the mixture for 5 minutes, maintaining the stirring rate at 300 rpm at 25 °C - the amount of silicone emulsion is that specified in table 1; (5) increase the stirring rate to 400 rpm, keeping the temperature at 25 °C, add the mancozeb so that it is added to the mixer during 1h and, immediately after the addition time (1h), keep stirring at 400 rpm at 25 °C for 30 minutes - the amount of mancozeb is that specified in table 1; (6) transfer the mixture from step (5) to a mill tank and grind for 90 minutes or until mancozeb particles with a diameter (dgs) between 2 and 7 microns are obtained, said grinding being carried out at 25 °C, and said grinding being carried out using a rotation frequency between 40 and 60 Hz; (7) verification of particle size in analyzer, and parallel control in 325 mesh; if the values ​​obtained meet the physical-chemical parameters of table 2, proceed to step (8); otherwise, repeat step (6); (8) adjust the viscosity and density of the formulation by adding 2-hydroxyethyl cellulose ether in an adequate amount to achieve the respective viscosity and density ranges described in Table 2; and adding 1,2-benzisothiazolin-3-one - the "adequate amount" of 2-hydroxyethyl cellulose ether is that which is equal to or less than that stated in Table 1, since there is a possibility that the aforementioned viscosity and density may be achieved in an amount less than that described in Table 1 for said thickener; the amount of 2-benzisothiazolin-3-one, in turn, is that specified in Table 1; (9) stir the mixture from step (8) for 15 minutes at a stirring rate of 300 rpm at 25 °C; obtaining the aqueous formulation of fungicide in concentrated suspension, said fungicide being mancozeb at a concentration of 445 g / L in water; and (10) carry out physical-chemical / chromatographic control of the formulation through quality control and subsequent approval, said approval being conditional on the formulation (product) meeting all physical-chemical parameters. chemicals described in Table 2.

[0077] The physical-chemical parameters mentioned in the description of steps (7), (8) and (10) are described in table 2, said parameters being used as quality control.

[0078] Table 2: physical-chemical parameters controlled in steps (7), (8) and (10).

[0079] The inventors of the present invention have discovered that in order for the surprising technical effect in field application to be achieved, the formulation must present the physicochemical parameters within the acceptance ranges described in Table 2. By "surprising technical effect" in the context of the present invention, it should be understood that this is the formulation described herein, which provides similar or better results than the prior art. Because it may have a technical effect similar to what already exists, the aqueous fungicide formulation in aqueous suspension also ends up being an alternative formulation for the end consumer (farmers, etc.), as said alternative aims to solve the problems of the prior art (already mentioned) by presenting the following technical solutions:

[0080] - presence of few adjuvants, known as low concentration adjuvants;

[0081] - absence of non-essential components such as preservatives, antifreeze and related products;

[0082] - absence of xanthan gum; and

[0083] - absence of components that are toxic to humans, the environment and living beings, such as those derived from petroleum (heavy aromatic solvents, naphthalene, paraffin, hydrocarbons in general, etc.).

[0084] Considering the above, even with the removal of key components, simplification of the formulation, reduction of adjuvant concentration, and removal of xanthan gum, the formulation obtained was still able to present agronomic performance equal to or better than that of the prior art. In attempting to obtain a formulation like this, a person skilled in the art would easily conceive of an inefficient formulation, since the removal of adjuvants and reduction in the concentration of those that remain favors the production of a product with low efficacy. Faced with this technical difficulty, the inventors of the present invention surprisingly conceived the formulation with the aforementioned characteristics while maintaining the application results expected by the consumer who benefits from this object of the present invention. These characteristics reflect the appropriate choice and quantity of each of the components, as well as the execution of an appropriate production process to obtain the formulation.

[0085] As one of the ways to better demonstrate the difference of the present invention, the physical-chemical stability tests of the aqueous fungicide formulation in concentrated suspension and their respective results achieved will be described below. Physicochemical stability studies

[0086] The objective of this study was to determine the thermal and air stability of the aqueous fungicide formulation in concentrated suspension, evaluating the active ingredient content after 14 days of incubation at 54 ± 2 °C. Experimental procedure Incubation of the formulation at 54 ± 2 °C

[0087] 62.0 g of the formulation was weighed into a bottle with a lid and then incubated at 54 ± 2 °C for a period of 14 days in the dark. Formulation kept at 25 ± 1 °C

[0088] 60.4 g of the formulation was weighed into a bottle with a lid and then kept at 25 ± 1 °C for a period of 14 days. Determination of the active ingredient Preparation of solutions

[0089] Lead acetate solution (10% m / v): 20.0013 g of lead acetate was weighed in a 100 ml flask, transferred to a 200 ml volumetric flask. It was dissolved and the volume was completed with ultrapure water.

[0090] Potassium hydroxide solution (2 mol.L 1 ): 56.1101 g of potassium hydroxide was weighed. It was dissolved in approximately 250 ml of methanol. After cooling, the solution was transferred to a 500 ml volumetric flask and the volume was adjusted with methanol. The solution was filtered through a vacuum pump system.

[0091] Ethanolic phenolphthalein solution (0.5% m / v): Approximately 0.253 g of phenolphthalein was weighed into a 50 ml volumetric flask. 30 ml of ethanol was added and the solution was homogenized. The volume was adjusted with ultrapure water.

[0092] Acetic acid solution (30% v / v): Approximately 60 ml of glacial acetic acid was diluted in a 200 ml volumetric flask. The volume was completed with ultrapure water and the solution was homogenized.

[0093] Tetrasodium EDTA solution (34% m / v): Approximately 38.9336 g of tetrasodium EDTA was weighed into a 100 ml flask, approximately 50 ml of ultrapure water was added, and the solution was homogenized. The solution was transferred to a 100 ml volumetric flask, and the volume was made up to volume with ultrapure water.

[0094] Sulfuric acid solution (1.1 N): Approximately 16.5 ml of sulfuric acid was diluted in a 500 ml volumetric flask. The volume was completed with ultrapure water and the solution was homogenized.

[0095] Starch solution (1% w / v): Approximately 2.0014 g of soluble starch was weighed into a 100 ml flask, and 20 ml of ultrapure water was added. The solution was transferred to a 250 ml flask containing approximately 20 ml of boiling ultrapure water, and the solution was homogenized. After cooling, the solution was transferred to a 200 ml volumetric flask, and the volume was adjusted with ultrapure water. Procedure

[0096] A condenser was connected to the distillation flask and cooled. Approximately 25 ml of lead acetate solution (10% m / v) was added to the first absorber. This absorber was connected to the distiller. Approximately 25 ml of methanolic potassium hydroxide solution (2 mol.L-1) were added to the second and third absorbers, and the glassware was cooled. The thermostatic bath water began to flow and the absorbers were interconnected.

[0097] Approximately 0.2 g (Table 3) of the formulation was weighed and transferred to a 250 ml decomposition flask. Approximately 10 ml of tetrasodium EDTA solution (34% w / v) was added to this flask, and the solution was stirred until the sample dispersed. The decomposition flask was connected to the condenser and placed on the heating mantle.

[0098] The top of the third absorber was connected to a vacuum pump, with a flow rate of 120–360 bubbles per minute. Then, approximately 50 ml of 1.1 N sulfuric acid solution was added at boiling point through the decomposition flask on the inlet side. The heating mantle was turned on, and when the solution became clear (lighter), the heating was reduced. Reflux was maintained for exactly 105 minutes from the start of heating. Then, the heating mantle was removed and the decomposition flask disconnected.

[0099] The absorbers containing the methanolic potassium hydroxide solution were disconnected, and their contents were transferred to 500 ml Erlenmeyer flasks using 250 ml of ultrapure water. Three drops of phenolphthalein (0.5% w / v ethanolic solution) were added to the Erlenmeyer flasks containing the final solution and neutralized with acetic acid solution (30% v / v). The neutralized solution was immediately titrated with iodine solution (0.1 N) until the color of the solution turned yellow. Then, 5 ml of starch solution (1% w / v) was added, and the titration was continued until the endpoint with a bluish color. This procedure was performed in triplicate. Calculations

[0100] The concentration of mancozeb (%Ci ( m / m)) in the formulation was calculated based on the equation below: %Ci (m / m) = [(AB) x N x 0.13551] / m - Equation 1, Where: Ci = concentration of Mancozeb in the formulation in % (m / m); A = volume of iodine solution consumed in the titration of the formulation (ml_); B = volume of iodine solution consumed in the blank titration (ml_); N = the molarity of the iodine solution = 0.1 N; Mancozeb factor = 0.13551; m = mass of the formulation (g). c2(gL-1) = %C1 (m / m) x 10 xd - Equation 2, where: d = density of the formulation (1.1972 g.cm' 3 ).

[0101] The degradation of the formulation resulting from incubation was calculated using the following equation: Df (%) = {[CAI25 — CAI54] / CAI2S} X 100 — Equation 3, where: Df - degradation of the formulation; CAI25 (formulation maintained at 25 ± 1°C) - average mancozeb content from the initial analysis of the formulation; and CAI54 (formulation incubated at 54 ± 2°C) - average mancozeb content of incubated samples of the formulation.

[0102] The arithmetic mean (p) was determined by the equation below: p = (xi + X2 + ... + x n) / n = 2xi / n - Equation 4, where: p = arithmetic mean of the values; Xi= values ​​obtained; en= number of values ​​obtained.

[0103] The standard deviation (s) was calculated according to the following equation: s = [Z(xi - p) / (nl)] 1 / 2 - Equation 5.

[0104] The relative standard deviation (RSD) was calculated according to the following equation: DPR% = (s / p) x 100 - Equation 6, where: s = standard deviation; ep = arithmetic mean of the values. Results

[0105] Table 3: Analysis of mancozeb in the formulation maintained at 25 ± 1 °C and 54 ± 2 °C.

[0106] Table 4 shows the degradation of the formulation, calculated from the determined mean of the mancozeb content in the formulation kept at 25 ± 1 °C and incubated at 54 ± 2 °C for 14 days.

[0107] Table 4: Degradation of mancozeb 445 SC after 14 days of incubation at 25 ± 1 °C and 54 ± 2 °C.

[0108] According to CIPAC MT 46.3 (2017) (Collaborative International Pesticides Analytical Council), the aqueous formulation of pesticide in concentrated suspension is considered stable at normal storage temperatures for a period of at least 2 years, if, following incubation for 14 days at 54 ± 2°C, its content characteristics remain unchanged or do not differ by more than 5% from the initial analysis. Example 3 Comparative physicochemical stability studies (reference RN 9530).

[0109] The present study aims to demonstrate the advantages of using 2% hydroxyethylcellulose over xanthan gum as a thickener in an aqueous fungicide suspension concentrate formulation. For a better understanding of the studies described below, the aqueous fungicide suspension concentrate formulation will be referred to hereinafter as the mancozeb 44.5% SC formulation.

[0110] A 6-liter formulation of mancozeb 44.5% SC was prepared and divided into two to cover a single variable, in this case the thickener. The formulations were designated M1 and M2, namely: - Ml: mancozeb 44.5% SC formulation with 2% hydroxyethylcellulose as thickener; and - M2: mancozeb 44.5% SC formulation with 2% xanthan gum as thickener.

[0111] Stability studies were conducted at temperatures of zero, 3 °C and 54 °C, where: - T=0: stability test at temperature and ambient conditions; - T=3°C: stability test in a climatic chamber at 3°C ​​for 7 days: simulates the climatic conditions of places with low temperatures; and - T=54°C: stability test in an oven at 54°C for 14 days: simulates shelf life conditions of approximately 2 years.

[0112] Table 5: Physicochemical results for the mancozeb formulation 44.5% SC containing hydroxyethylcellulose.

[0113] Table 6: Physicochemical results for the mancozeb formulation 44.5% SC containing xanthan gum.

[0114] As noted, no difference is displayed immediately. However, there are significant differences in stability results, particularly at 54°C. As known by a person skilled in the art, Mancozeb exhibits a significant increase in viscosity at high temperatures, so that at 54°C, it is very difficult for the product to flow smoothly, with low viscosity. As can be seen in M1, viscosity can be measured, which is not the case in M2. Quarantine results

[0115] For quarantine control, formulations M1 with hydroxyethylcellulose and M2 with xanthan gum are divided into individual vials that are stored at room temperature and remain undisturbed for 6 months until the control date. The quarantine control configuration is described in Table 7.

[0116] Table 7: Configuration for quarantine controls of M1 and M2 formulations.

[0117] Viscosity control measured in seconds is performed at Ford Cup No. 4. The reference standards for this test are as follows: -VISCOSITY CIPAC MT 22; and -IRAM 1109-A14 VISCOSITY DETERMINATION WITH THE FORD CUP. Results

[0118] Initially a bottle is opened weekly, and after a month the The vial is evaluated monthly. Both formulations were evaluated until the sixth month, and the results are compiled in Table 8 below. As noted, although in M1 (HEC as a thickener) the viscosity increases over time, this viscosity increase remains fixed and can be measured constantly, and the product remains fluid. In M2 (xanthan gum as a thickener), on the other hand, the viscosity increases much more almost immediately and can no longer be measured by the fourth week.

[0119] Table 8: Quarantine test results for formulations M1 and M2. Conclusion

[0120] As explained, the mancozeb 44.5% SC formulation with hydroxyethylcellulose as a thickener is a more stable product than the mancozeb 44.5% SC formulation with xanthan gum. This is because the viscosity with hydroxyethylcellulose remains lower and more stable over time compared to the formulation containing xanthan gum. This is observed in the stability results at 54°C, where the sample viscosity was so high that it could not be measured, while the results of the sample with hydroxyethylcellulose showed more stable values. The same can be said observed in the quarantine results, in which the sample with xanthan gum showed very high viscosity values ​​and by the fourth week it was so high that it could no longer be measured. In the sample with hydroxyethylcellulose, on the other hand, this remained with reduced viscosity and was more stable during the 6 months of testing.

[0121] It should be understood that the present description does not limit the application to the details described herein and that the invention is capable of other embodiments and of being practiced or executed in a variety of ways, within the scope of the claims. Although specific terms have been used, such terms should be construed in a generic and descriptive sense, and not for the purpose of limitation.

Claims

CLAIMS 1. Aqueous formulation of fungicide in concentrated suspension, characterized by the fact that it comprises the following components, in percentage by mass (% m / m): (a) 30 to 50% of a dithiocarbamate fungicide; (b) 0.1 to 3% of an aliphatic ethoxylated alcohol of formula (I) Ri-O-(CH2CH2O)nH (I), where Ri is a linear or branched C8-C25 alkyl chain and "n" varies from 1 to 10; (c) 0.1 to 3% of a block copolymer of polyethylene glycol and polypropylene glycol of formula (II) H-[OCH2CH2]x[OCH(CH3)CH2] y [OCH2CH2]x-OH (II), where "x" varies from 80 to 135 and "y" varies from 30 to 70; (d) 0.1 to 2% of a cellulose derivative; (e) 0.1 to 3% of an antifoam; and (f) 50 to 65% water, said formulation being free of any of the following components: (A) polysaccharide gum; (B) naphthalene derivatives; (C) pH regulators; (E) antifreeze; (F) hydrocarbons derived from petroleum; (G) lignosulfonate salts; and (H) formaldehyde.

2. Formulation according to claim 1, characterized in that the components are present in the following amounts (% m / m): (a) 35 to 45% of the fungicide dithiocarbamate; (b) 0.8 to 1.5% of the aliphatic ethoxylated alcohol of formula (I); (c) 0.8 to 1.5% of the block copolymer of polyethylene glycol and polypropylene glycol of formula (II); (d) 0.1 to 1% of cellulose derivative; (d) 0.1 to 1% of the defoamer; and (e) 55 to 60% of water.

3. Formulation according to claim 1, characterized in that the components are present in the following amounts (% w / w): (a) 38.2% of the fungicide dithiocarbamate; (b) 1.3% of the aliphatic ethoxylated alcohol of formula (I); (c) 1.4% of the block copolymer of polyethylene glycol and polypropylene glycol of formula (II); (d) 0.2% of cellulose derivative; (d) 0.9% of the antifoam; and (e) 58% of water.

4. Formulation according to any one of claims 1 to 3, characterized in that Ri is a linear C10-C20 alkyl chain, "n" ranges from 1 to 6, "x" ranges from 90 to 110, and "y" ranges from 55 to 70.

5. Formulation according to any one of claims 1 to 4, characterized in that Ri is a linear C12-C16 alkyl chain, "n" ranges from 1 to 3, "x" ranges from 95 to 100, and "y" ranges from 62 to 67.

6. Formulation according to any one of claims 1 to 5, characterized in that it additionally comprises a preservative in amounts between 0.001 and 0.01% by mass (% w / w).

7. Formulation according to claim 6, characterized in that the preservative is present in an amount of 0.005% by mass (% m / m).

8. Formulation according to any one of claims 1 to 7, characterized in that the dithiocarbamate is selected from the group comprising mancozeb, maneb, metiram, propineb, zineb, amobam, ferbam, tiram or ziram.

9. Formulation according to any one of claims 1 to 8, characterized in that the dithiocarbamate is mancozeb.

10. Formulation according to any one of claims 1 to 9, characterized in that the cellulose derivative is selected from the group comprising methyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, hydroxyethyl carboxymethyl cellulose, carboxymethyl cellulose or carboxymethyl hydroxyethyl cellulose.

11. Formulation according to any one of claims 1 to 9, characterized in that the cellulose derivative is hydroxyethyl cellulose.

12. Formulation according to any one of claims 6 to 11, characterized in that the preservative is selected from the group comprising 2-methyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one or n-octyl-isothiazolin-3-one.

13. Formulation according to any one of claims 6 to 12, characterized in that the preservative is 1,2-benzisothiazolin-3-one.

14. Formulation according to any one of claims 1 to 13, characterized in that the polysaccharide gum is selected from the group comprising xanthan gum, guar gum, locust bean gum, gum Tragacanth, gum arabic, gellan gum, carrageenan gum, ghatti gum or karaya gum.

15. Formulation according to any one of claims 1 to 14, characterized in that the polysaccharide gum is xanthan gum.

16. Formulation according to any one of claims 1 to 15, characterized in that the naphthalene derivatives are selected from the group comprising naphthalene, naphthalene sulfonic acid condensate with formaldehyde, diisopropyl naphthalene sulfonic acid condensate with formaldehyde, alkyl naphthalene sulfonic acid condensate with formaldehyde, naphthalene sulfonic acid, sodium naphthalene sulfonate, diisopropyl naphthalene sulfonic acid, sodium diisopropyl naphthalene sulfonate, alkyl naphthalene sulfonic acid or sodium alkyl naphthalene sulfonate.

17. Formulation according to any one of claims 1 to 16, characterized in that the naphthalene derivatives are the condensate of naphthalene sulfonic acid with formaldehyde, naphthalene sulfonic acid or sodium naphthalene sulfonate.

18. Formulation according to any one of claims 1 to 17, characterized in that the pH regulators are selected from the group comprising propionic acid, sorbic acid, benzoic acid, citric acid, lactic acid or acetic acid.

19. Formulation according to any one of claims 1 to 18, characterized in that the pH regulators are citric acid.

20. Formulation according to any one of claims 1 to 19, characterized in that the antifreezes are antifreeze glycols.

21. Formulation according to claim 20, characterized in that the antifreeze glycols are selected from the group comprising propylene glycol, ethylene glycol, polyethylene glycol or glycerol.

22. Formulation according to claim 20, characterized in that the antifreeze glycols are ethylene glycol or polyethylene glycol.

23. Formulation according to any one of claims 1 to 22, characterized in that the petroleum-derived hydrocarbons are selected from the group comprising aromatic solvents, naphthalenic solvents, naphthalenic oils or paraffinic oils.

24. Formulation according to any one of claims 1 to 23, characterized in that the lignosulfonate salts are selected from the group comprising sodium, calcium or ammonium lignosulfonate.

25. Formulation according to any one of claims 1 to 24, characterized in that the lignosulfonate salts are sodium lignosulfonate.

26. Process for producing the aqueous fungicide formulation in concentrated suspension defined in any one of claims 1 to 25, characterized in that it comprises the following steps: (a) in a formulating tank, add water and start stirring using a mixer; (b) add the aliphatic ethoxylated alcohol of formula (I) to the water and continue stirring; obtaining a first mixture; (c) add the polyethylene glycol and propylene glycol block copolymer of formula (II) to the first mixture and continue stirring; obtaining a second mixture; (d) add the antifoaming agent to the second mixture and keep stirring; obtaining a third mixture; (e) add the dithiocarbamate to the third mixture, said addition being carried out between 30 and 120 minutes, and maintain stirring after the time of addition of said dithiocarbamate; obtaining a fourth mixture; (f) grinding the fourth mixture for 60 to 180 minutes, said grinding being carried out at temperatures between 20 and 30 °C, and said grinding being carried out at a rotation frequency between 20 and 80 Hz; obtaining a ground mixture comprising microparticles of dithiocarbamate; (g) carrying out a preliminary quality control of the ground mixture, said quality control comprising a particle size analysis (dgs) and a 325 mesh test for dithiocarbamate microparticles; (h) decision on repeating step (f) or proceeding with step (i), said decision being based on the following conditions: if the particle size (dgs) is outside the range between 2 and 7 microns, repeat step (f); if the particle size (dgs) is between 2 and 7 microns and the 325 mesh test shows zero or negligible retention of said microparticles, proceed with step (i); (i) add the cellulose derivative and the preservative to the mixture approved in step (h), and start stirring; obtaining the aqueous fungicide formulation in concentrated suspension; and (j) carrying out a general quality control comprising the measurement of physicochemical parameters selected from the group comprising color, pH, density, foam appearance, viscosity, particle size, 325 mesh test, 200 mesh test, suspension level, mancozeb content and stability at 54 °C.

27. Process, according to claim 26, characterized by the fact that the agitation in steps (a), (b), (c), (d), (e) and (i) is carried out at speeds between 300 and 800 rpm, said agitation being carried out at a temperature of 13 to 37 °C.

28. The process of either claim 26 or 27, characterized by the fact that: the stirring in steps (a), (b) and (c) is carried out for 1 to 40 minutes; the stirring in step (d) is carried out for 1 to 20 minutes; the stirring in step (e) is carried out for 3 to 120 minutes; and the stirring in step (i) is carried out for 1 to 60 minutes.

29. Process, according to claim 26, characterized by the fact that: the agitation in steps (a), (b) and (c) is carried out for 10 minutes; the agitation in step (d) is carried out for 5 minutes; the agitation in step (e) is carried out for 30 minutes; and the agitation in step (i) is carried out for 15 minutes, wherein the agitation in steps (a), (b), (c), (d), (e) and (i) is carried out at speeds between 300 and 400 rpm, said agitation being carried out at a temperature of 25 °C.

30. Process according to any one of claims 26 to 29, characterized in that: in step (a) water is added in amounts between 55 and 60% (w / w); in step (b) the aliphatic ethoxylated alcohol of formula (I) is added in amounts between 0.8 and 1.5% (w / w); in step (c) the block copolymer of polyethylene glycol and propylene glycol of formula (II) is added in amounts between 0.8 and 1.5% (w / w); in step (d) the antifoam is added in amounts between 0.1 and 1% (w / w); in step (e) the dithiocarbamate is added in amounts between 35 and 45% (w / w); and in step (i) the cellulose derivative is added in amounts between 0.1 and 1% (m / m); and the preservative is added in quantities between 0.001 and 0.01% by mass (m / m).

31. Process according to any one of claims 26 to 29, characterized in that: in step (a) water is added in an amount of 58% (m / m); in step (b) the aliphatic ethoxylated alcohol of formula (I) is added in an amount of 1.3% (m / m); in step (c) the block copolymer of polyethylene glycol and propylene glycol of formula (II) is added in an amount of 1.4% (m / m); in step (d) the antifoam is added in an amount of 0.9% (m / m); in step (e) the dithiocarbamate is added in an amount of 38.2% (m / m), said addition being carried out over 60 minutes; in step (f) milling is carried out for 90 minutes at a temperature of 25 °C and at a rotation frequency between 40 and 60 Hz; and in step (i) the cellulose derivative is added in an amount of 0.2% (m / m); and the preservative is added in an amount of 0.005% by mass (m / m).

32. Use of the aqueous fungicide formulation in concentrated suspension defined according to any one of claims 1 to 25, characterized by the fact that it is for application to biological targets present in crops selected from the group comprising rice, banana, potato, citrus, beans, apple, corn, rose, soybean, tomato, wheat, grape, sugar cane or cotton.

33. Use according to claim 32, characterized in that the biological targets are selected from the group comprising Pyricularia grisae, Mycosphaerella musicola, Mycosphaerella fijiensis, Alternaria solani, Phytophthora infestans, Phyllocoptruta oleivora, Diaporthe citri, Elsinoe australis, Colletotrichum lindemutianum, Venturia inaequalis, Colletotrichum gloeosporioides, Phaeosphaeria maydis, Diplocarpon rosae, Septaria glycines, Corynespora cassiicola, Alternaria solani, Bipolaris sorokiniana, Plasmopora viticola, Greeneria uvicola, Phakopsora pachyrhizi, Colletotrichum truncatum, Thielaviopsis paradoxa, Puccinia Kuehnii, Puccinia polysora, Cercospora zeae maydis, Corynespora cassiicola or Ramularia areola.